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CN105121017B - Use steam activation hydrotreating catalyst - Google Patents

Use steam activation hydrotreating catalyst Download PDF

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Publication number
CN105121017B
CN105121017B CN201480021938.XA CN201480021938A CN105121017B CN 105121017 B CN105121017 B CN 105121017B CN 201480021938 A CN201480021938 A CN 201480021938A CN 105121017 B CN105121017 B CN 105121017B
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particle
calcining
self
activation
catalyst
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CN105121017A (en
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O·K·布汉
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

By making self-activation hydrotreating catalyst contact further self-activation catalyst of the activation for handling heavy hydrocarbon feedstocks with steam.The steam can be added to before being contacted with the self-activation catalyst in the heavy hydrocarbon feedstocks, or may be added to that in the reactor vessel containing self-activation catalyst.

Description

Use steam activation hydrotreating catalyst
The present invention relates to the self-activation hydrotreating catalysts that further activation uses in heavy hydrocarbon feedstocks processing.
Crude oil refining in, including residue heavy distillat usually by desulfurization, denitrogenation, demetalization or asphalitine conversion or its It arbitrarily combines and is subjected to catalytic hydrogenation treatment to remove component, such as sulphur, nitrogen, metal and Kang Laxun (Conradson) carbon.It is various Heterogeneous hydrotreating catalyst is by making under conditions of elevated temperature and pressure and in presence of hydrogen catalyst and charging Contact, to promote these reactions.
The one kind developed recently has excellent catalytic activity and stability and it is made to be highly suitable for processing heavy hydrocarbon feedstocks Hydrotreating catalyst is self-activation hydrotreating catalyst.Such as the U. S. application the 13/th that on October 25th, 2012 submits This self-activation catalyst is described in No. 660879, the U. S. application is incorporated herein by reference of text.
Still it is intended to provide and improves the active means of hydrotreating catalyst and method.
Therefore it provides the method for activating the self-activation hydrotreating catalyst used in handling heavy hydrocarbon feedstocks, Middle this method includes that self-activation hydrotreating catalyst is made to be contacted with steam.
Fig. 1 is illustrated in the case where addition is not with steam is added, the total sulfur conversion ratio of self-activation hydrotreating catalyst To the figure of running length in hours.Shown data point is the total sulfur in the residue charging at different time during operation Convert weight %.
Fig. 2 is illustrated in the figure of addition and micro- carbon residue (MCR) conversion ratio in the case of not adding steam.Shown data Point is the MCR conversion weight % at different time during operation.
Although having been shown that above-mentioned self-activation hydrotreating catalyst has excellent hydroprocessing activity, now It is found that the activity of these self-activation catalyst can be further increased by these catalyst are exposed to steam.
It is this to be surprisingly found that the base for constituting the method for the present invention for activating self-activation hydrotreating catalyst Plinth, this method include that self-activation catalyst described below is made to be contacted with steam.Preferably, (or steam can be converted to steam Water) addition or be introduced in the heavy hydrocarbon feedstocks then contacted with self-activation catalyst.Also steam can be directly introduced into containing In the reactor vessel of self-activation catalyst.The amount of the steam contacted with self-activation catalyst can change, but it is based on charging Weight meter is usually within the scope of 0.01wt.% to 10wt.%.Preferably, the amount of the steam contacted with self-activation catalyst is based on Feed weight meter is within the scope of 2.0wt.% to 6.0wt.%.Steam itself can be added in charging, or can be with the shape of water Formula is added, and water will be converted into steam at the raised temperature of charging.Also steam can be introduced directly into containing self-activation catalyst Reactor vessel in.
The additional active brought by making self-activation catalyst be contacted with steam is extremely beneficial, because it can lead Cause from polluted containing nitrogen, sulphur, asphalitine, micro- carbon residue (MCR) or Conradson carbon residue (CCR) and metal or by these components into Material obtains, and there is the required temperature of reactor of the product of these given constituent contents to reduce.It is relatively low caused by the activity of raising Temperature of reactor save the energy and catalyst life will be extended.
The self-activation hydrotreating catalyst that can be further activated using steam according to the method for the present invention, which is generally comprised, to be passed through The particle through calcining for including co-milled mixtures of following steps manufacture：By inorganic oxide powder, molybdenum trioxide powder and Nickel compound is co-mulled and made into, and so that co-milled mixtures is formed particle, thus calcining particle is to provide the particle through calcining.The warp The particle of calcining includes based on metal and the total weight based on the particle through calcining is within the scope of 1 weight % to 10 weight % The existing molybdenum of amount, and so that nickel existing for amount of the weight ratio less than 0.4 of the p- molybdenum of nickel-.The particle through calcining also has Following pore-size distribution：So that diameter existsExtremelyIn range Kong Zhanjing calcining particle total pore volume it is small In 70%, diameter existsExtremelyAt least the 10% of the total pore volume of the particle of Kong Zhanjing calcinings in range, and And diameter is more thanKong Zhanjing calcining particle total pore volume 1% to 10%.
The self-activation that the activation method of the present invention is used especially for using in further activation heavy hydrocarbon feedstocks hydrotreating adds Hydrogen handles catalyst, which has sulphur, nitrogen, metal such as vanadium and nickel and the Kang Laxun carbon of notable concentration and micro- carbon Residue carbon.Self-activation hydrotreating catalyst is unique in that when it is used to handle hydrocarbon charging, activity actually with Using and increase.In contrast, the hydrotreating catalyst activity of most of prior art is tended to decline with use.
Add at hydrogen it has been found that further increasing this self-activation by so that self-activation catalyst is contacted with steam Manage the activity of catalyst.This is very surprising, it is considered that wait for a large amount of water present in the hydrocarbon charging of hydrotreating or Steam is harmful for catalyst performance, because it can cause metal sintering and coalescence and catalyst surface area to be lost.
Can include inorganic oxide powder, three oxygen by the self-activation hydrotreating catalyst that the method for the present invention further activates Change the co-milled mixtures of molybdenum powder and nickel compound, wherein co-milled mixtures have been formed into particle, which is calcined Thus to provide the particle through calcining.The particle through calcining also has the aperture specifically limited described elsewhere herein point Cloth.The particle through calcining itself can be used as self-activation hydrotreating catalyst or can be used as its component.
Particle through calcining generally comprises inorganic oxide, molybdenum and nickel, wherein based on metal regardless of its actual form such as What, 1 weight % to 10 weight % (wt.%) range of the molybdenum content of the particle through calcining in the total weight of the particle through calcining It is interior, or, in other words, molybdenum content is 1.5wt.% to 15wt.% molybdenum trioxides (MoO3)。
It is expected that molybdenum is less than 9.5wt.% (that is, with MoO in the particle through calcining3Count 14.25wt.%) and at least 1.5wt.% is (that is, with MoO3Count 2.25wt.%) amount exist.In a preferred embodiment, molybdenum is in the particle through calcining Concentration in 2wt.% to 9wt.% (that is, with MoO3Count 3wt.% to 13.5wt.%) in range, and more preferably implementing In mode, the concentration is in 2.5wt.% to 8.5wt.% (that is, with MoO3Count 3.75wt.% to 12.75wt.%) in range.Molybdenum Most preferable concentrations ranging from 3wt.% to 8wt.% in the particle through calcining of the present invention is (that is, with MoO3Count 4.5wt.% To 12wt.%).
One importance of the self-activation catalyst further activated by the method for the invention is the particle through calcining Nickel with special low concentration so that the weight ratio of the p- molybdenum of nickel-is at least or more than 0.01 in the particle through calcining:1.Into One step it is expected that the weight ratio of the p- molybdenum of nickel-in the particle through calcining is less than 0.4:1.In general, the p- molybdenum of nickel-in the particle through calcining Weight ratio is 0.01:1 to 0.35:In 1 range.The weight ratio of the p- molybdenum of nickel-of particle through calcining is preferably 0.01:1 to 0.3: In 1 range.The weight ratio is calculated and is provided based on simple substance.
It is indicated with atomic ratio, the particle through calcining should have at least or be more than 0.01:The atomic ratio of the 1 p- molybdenum of nickel-.It can Further it is expected that the atomic ratio of the p- molybdenum of nickel-in the particle through calcining is less than 0.4:1.In general, the nickel-in the particle through calcining The atomic ratio of p- molybdenum is 0.01:1 to 0.35:In 1 range, and preferably, in the range, the nickel-of the particle through calcining The atomic ratio of p- molybdenum is 0.01:1 to 0.3:In 1 range.
The amount of the inorganic oxide of particle through calcining can be in the range of the at most about 98 weight % of the particle through calcining. Typically, the inorganic oxide of the particle through calcining is with the 70 weight % to 98 weight % and preferably 75 weights of the particle through calcining Measure the amount presence in the range of % to 98 weight %.
It can be it is also expected to the particle through calcining be substantially free of cobalt.Although and do not know, but it is believed that in the particle through calcining The cobalt of the amount of existing substance may negatively affect the self-activation property of composition, therefore when the particle through calcining is for adding When the heavy hydrocarbon feedstocks of nickel of the hydrogen processing with certain concentration, should not exist in the particle through calcining may negatively affect its self-activation The cobalt of the amount of property.
Term " being substantially free of cobalt " in this article refers to composition and contains cobalt (if any), institute with such concentration It states concentration and makes the heavy feedstocks for hydrotreating (for example, hydrodesulfurization) when the particle through calcining with the nickel of certain concentration When, not its self-activation attribute of substantial effect.Heavy feedstocks and nickel concentration limiting in detail elsewhere in this paper.
It is substantially free of cobalt typically to refer to, calculates by metal and total weight based on the particle through calcining is regardless of cobalt How is actual form, and the particle through calcining may include the cobalt less than 0.1 weight % (wt.%).Preferably, cobalt is to be less than The concentration of 0.075wt.% and more preferably less than 0.05wt.% are stored in the particle through calcining.It also can be substantially through calcining particle Without cobalt.
One important feature of the self-activation catalyst that can be further activated using steam according to the method for the present invention is them Pore structure.It is believed that when the particle through calcining is for the nickel of hydrotreating hydrocarbon charging, especially hydrotreating with certain concentration When heavy hydrocarbon feedstocks, specific pore structure and the combination of relatively low intensity of nickel as defined herein provides the particle through calcining Unique self-activation feature.Think to be more thanMacropore account for total pore volume substantial but only of the particle through calcining Big percentage andExtremelyMedium sized mesoporous in range accounts for the opposite large scale of total pore volume In the presence of providing contributes to mechanism described above, and allows nickel to migrate and be transported to the suitable of suitable position in the hole of composition Work as structure.
It is also important that diameter is more than in the pore structure of the particle through calciningHole account for total pore volume at least 1%.Moreover, diameter is more than in the particle through calciningKong Zhanqi total pore volumes be less than 10%.Preferably, directly Diameter is more thanKong Zhanjing calcinings particle total pore volume 2% to 10%, and it is highly preferred that diameter is more thanKong Zhanjing calcining particle total pore volume 3% to 9%.
About the median size mesoporous of the particle through calcining, diameter existsExtremelyKong Zhanjing in range is forged The total pore volume of the particle of burning at least 40% but be less than 70%.Preferably, diameter existsExtremelyHole in range Account for the 50% to 70% of the total pore volume of the particle through calcining.
It is also expected to diameter existsExtremelyThe total pore volume of the particle of Kong Zhanjing calcinings in range is at least 10%.Preferably, diameter existsExtremelyThe total pore volume of the particle of Kong Zhanjing calcinings in range is at least 15%, at least 20% is more preferably accounted for.
In the preparation of the self-activation catalyst further activated using steam according to the method for the present invention, starting material is preferred It is mixed by being co-mulled and made into, to form co-milled mixtures.In the preparation of co-milled mixtures, necessary starting material includes Molybdenum trioxide preferably can be the fine particle form of dried powder or the particle being present in suspended substance or slurry, Nickel component and inorganic oxide material.The optional self-alumina of inorganic oxide material, silica and alumina silica.
Nickel component, which can be selected to be mixed and formed into the other components of co-milled mixtures, waits for calcining to form this hair The arbitrary of the particle of the bright particle through calcining is suitble to nickel compound.Nickel component can be the nickel of oxide form, such as nickel oxide, Or can be nickel salt compound.Oxidation nickel compound applicatory includes, for example, the hydroxide of nickel, nitrate, acetate And oxide.A kind of preferred nickel compound that can be used for preparing co-milled mixtures is nickel nitrate.
The formation of co-milled mixtures can by any method known to those skilled in the art or means complete comprising But it is not limited to using the solid blender for being suitble to type, such as rotary drum, set casing or slot type, grinding formula mixing machine, (it is batch-type Or continuous type) and impact mixer, and using for hybrid solid and liquid or being used to form extrudable paste and mix The batch-type or continuous mixing machine of the suitable type of object.It includes but not limited to change pot type to mix to be suitble to the batch mixer of type Conjunction machine, the double-arm kneading machine for fixing trough-type mixture machine, the mixing blade for being equipped with any suitable type.It is suitble to the continous way of type Mixing machine includes but not limited to single or double screw extruder, slot-screw mixer (trough-and-screw mixer) and practices Mud machine (pug mill).
Required for the mixing of the starting material of particle through calcining can suitably homogenize into co-milled mixtures are exercised Any suitable period.In general, in the range of blending time can be at most 2 hours or more than 3 hours.Typically, it admixes Time is within the scope of 0.1 hour to 3 hours.
Term " being co-mulled and made into " widely used in the present specification refers to that the starting material that will be at least described is blended in one It rises to form the mixture of each component of co-milled mixtures, is preferably the base of each component of this co-milled mixtures Uniform or homogeneous mixture in sheet.It is wide in range enough that the term is intended to range, to include mixing starting material to generate performance Going out can be extruded as or be configured to squeeze out the paste of the property of composition granule by arbitrary known extrusion method.But it should Term is also aimed to including by any means well known by persons skilled in the art comprising but be not limited to molding, briquetting, compacting, Granulation is squeezed out and is overturn and mixes starting material, and to generate mixture, which homogeneous and can preferably substantially coalesce For molding particle, such as spherical, pellet or sheet, cylindric, irregular extrudate or the aggregation or cluster only loosely bonded.
As already noted, one of the self-activation catalyst further activated using steam according to the method for the present invention is important Aspect is that at least most of molybdenum source of the particle through calcining is mainly molybdenum trioxide.In the starting material of the particle through calcining The mixing of material is co-mulled and made into, and preferably molybdenum trioxide is as fine grain thin in fine powder solid or suspended substance or slurry Broken state.It is best the grain sizes of the molybdenum trioxide particles for manufacturing catalyst to have and be less than 0.5mm's (500 microns, μm) The full-size of full-size, preferably less than 0.15mm (150 μm), even more preferably less than 0.1mm (100 μm), and it is optimal Selection of land is less than 0.075mm (75 μm).
Although and do not know, it is believed that used in the self-activation catalyst further activated by the method for the invention three Molybdenum oxide is that the upper particle form as small as possible of practice is advantageously；Therefore, it is not intended that being used in the particle manufacture through calcining Molybdenum trioxide particles size have lower limit.It should be understood, however, that the molybdenum trioxide used in the particle manufacture through calcining Grain size will generally have the lower limit for the size for being more than 0.2 micron.Therefore, in the manufacture of particle of the present invention through calcining, The grain size of the molybdenum trioxide used in the formation of co-milled mixtures is preferably at 0.2 μm to 150 μm, more preferably at 0.3 μm to 100 μm and most preferably in 0.5 μm to 75 μ ms.Typically, it is in three oxidations of dried powder or suspended substance or other forms The size distribution of molybdenum particle makes at least 50% particle have the full-size in 2 μm to 15 μ ms.
Once the starting material of the particle through calcining suitably mixes and is formed as the particle shaped or shaped, can be advantageous Ground removes a certain amount of water or volatile matter that co-milled mixtures or shaped particles include using drying steps.Shaped particles Drying can for remove excessive water or volatile matter it is arbitrary be suitble to temperature under carry out, it is preferable that drying temperature will Within the scope of about 75 DEG C to 250 DEG C.Period for dry particle is the volatile content for making particle before calcining step Reduce the desired amount required arbitrarily suitable period.
Dried or undried particle is forged in the presence of oxygen-bearing fluid such as air being adapted for carrying out expectation It is calcined at a temperature of burning degree.In general, calcination temperature is in 450 DEG C (842 °F) to 900 DEG C of (1652 °F) ranges.Calcining The temperature condition of particle may be important for controlling the pore structure of the particle through calcining.Since there are three oxygen in shaped particles Change molybdenum, provides the required calcination temperature of the particle through calcining with required pore structure higher than other are calcined and contain inorganic oxide The composition of object material, particularly without the required representative temperature of those of molybdenum trioxide.But anyway, control is forged Shaped particles are burnt to provide the temperature of the particle through calcining, to provide with pore structure property as described in detail herein Particle through calcining.Preferred calcination temperature most preferably exists in 510 DEG C (950 °F) to 820 DEG C of (1508 °F) ranges In 700 DEG C (1292 °F) to 790 DEG C of (1454 °F) ranges.
It is acted on high-content pitch, organic metal such as including the particle through calcining of self-activation catalyst is especially useful High-activity hydrogenation catalyst in the hydrotreating of the heavy feedstocks stream of nickel and vfanadium compound and sulphur.Particle through calcining exists It can cure before, but not be required.In general, in hydrotreating of the self-activation catalyst for hydrocarbon charging, quilt It is contained in reaction zone, such as the reaction zone defined by reactor vessel, wherein making under the conditions of suitable hydrotreating reaction Hydrocarbon charging is contacted with self-activation catalyst, and thus generates processed hydrocarbon products.
According to the method for the present invention, it after self-activation catalyst is placed in reaction zone and is contacted with hydrocarbon charging, is urged by making Agent contacts with steam and further activates self-activation catalyst.This can be by making charging contact it with self-activation catalyst Steam is added in forward direction hydrocarbon charging or by being added directly to steam in the reactor vessel containing self-activation catalyst come side Just it completes.Steam addition can be started in the random time when operation starts or after bringing into operation.Although in operation very Later stage obtains the benefit of steam activation when adding steam, but whole benefits of steam activation in order to obtain, preferably steam are added Quite early stage in operation, i.e., occur in first week.
Preferred hydrocarbon charging for activation method of the present invention is heavy hydrocarbon feedstocks.Heavy hydrocarbon feedstocks can derive from arbitrary higher boiling temperature Spend petroleum distillate, such as atmospheric tower gas oil, atmospheric tower bottoms object, vacuum tower gas oil and vacuum tower bottoms object or residual oil.This One particularly useful aspect of inventive method is to provide the hydrotreating of heavy hydrocarbon feedstocks, which can usually be limited to have There is the boiling temperature (i.e. T (5)) more than 300 DEG C (572 °F) at its 5% distillation point, as by using institute in ASTM D-1160 What the test program stated was measured.The present invention relates more particularly to have more than 315 DEG C (599 °F) and even more than 340 DEG C The hydrotreating of the heavy hydrocarbon feedstocks of the T (5) of (644 °F).
Heavy hydrocarbon feedstocks may also include the heavier hydrocarbon that boiling temperature is higher than 538 DEG C (1000 °F).These heavier hydrocarbons are herein Referred to as pitch, and as already noted, it is understood that one of catalyst of the present invention or method be especially characterized in its heavy hydrocarbon into It is particularly effective in terms of the hydro-conversion of the bitumen content of material.Heavy hydrocarbon feedstocks may include as little as 10 volume % pitches or up to 90 bodies Product % pitches, but the amount for the pitch that usually heavy hydrocarbon feedstocks include is within the scope of 20 volume % to 80 volume %.In addition, more allusion quotation Type, the bitumen content in heavy hydrocarbon feedstocks is within the scope of 30 volume % to 75 volume %.
For further activate the self-activation catalyst fed for hydrotreatment of heavy hydrocarbon the method for the present invention another Especially be characterized in its make charging in micro- carbon residue (MCR) significantly reduce, for example, from the absence of steam 8% reduce to 3% or lower in the presence of steam.MCR is measured by using test method ASTM D-4530.
Heavy hydrocarbon feedstocks may also include quite high sulfur content.One of activation method of the present invention is especially characterized in that it makes heavy hydrocarbon Feed desulfurization and demetalization.The sulfur content of heavy hydrocarbon feedstocks is mainly sulfur-containing organic compound form, may include such as mercaptan, warp The sulfur-containing compound of thiophene, heterocyclic compound or any other type for replacing or being unsubstituted.
One feature of the method for the present invention for further activating self-activation catalyst, which is it, makes have quite high sulphur Content, such as it is typically greater than the heavy feedstocks desulfurization of the sulfur content of 1 weight %, to provide with the sulfur content reduced, example The processed hydrocarbon products of such as less than 1 weight %, preferably smaller than 0.75wt.% and the more preferably less than sulfur content of 0.5wt.%.
When the sulfur content of heavy hydrocarbon feedstocks or processed hydrocarbon products is mentioned above, weight % is by using test method ASTM D-4294 are measured.
The method of the present invention for activating self-activation catalyst is used especially for the heavy hydrocarbon that processing sulfur content is more than 2 weight % Charging, and for this heavy hydrocarbon feedstocks, sulfur content can be within the scope of 2 weight % to 8 weight %.Activation method of the present invention is special Can be used for handling has more than 3 weight % or even 4 weight % and in 3 weight % to 7 weight % or even 4 weight % to 6.5 The heavy hydrocarbon feedstocks of extra high sulfur content within the scope of weight %.
The method of the present invention for activating self-activation catalyst be suitable for hydrotreatment of heavy hydrocarbon charging with provide and meanwhile desulfurization, Denitrogenation, the micro- carbon residue of conversion and removing vanadium and nickel.In the method, under suitable hydrodesulfurization and hydro-conversion treatment conditions So that heavy hydrocarbon feedstocks and steam is contacted with catalyst of the present invention, generates processed hydrocarbon products.
One embodiment of the method for the present invention is the heavy hydrocarbon feedstocks of nickel of the processing with notable concentration, and such as institute above Point out, the important feature of the embodiment of the method for the present invention be activation with unique physical characteristics and special metal load with And the combination of the self-activation catalyst of relatively low nickel content and the heavy hydrocarbon feedstocks with notable nickel content.It is believed that with nickeliferous Using the self-activation catalyst with low nickel content in the processing of heavy hydrocarbon feedstocks, the activity of catalyst improves, because coming from heavy hydrocarbon The nickel deposition of charging absorbs on a catalyst or by catalyst.
Therefore, what the nickel content of the heavy hydrocarbon feedstocks of the method for the present invention had some concentration is usually organo-nickel compounds form Pollutant nickel.The nickel concentration of heavy hydrocarbon feedstocks typically can be within the scope of 1ppmw to 250ppmw.It is expected that the method for the present invention Hydrocarbon charging has the nickel concentration within the scope of 5ppmw to 225ppmw, and more desirable nickel concentration is in 7ppmw to 200ppmw ranges It is interior.
Heavy hydrocarbon feedstocks can also have typically can be in the vanadium concentration within the scope of 5ppmw to 250ppmw.It is expected that heavy hydrocarbon feedstocks contain There is vanadium as few as possible, but the method for the present invention provides demetalization, and therefore can provide and remove vanadium from heavy hydrocarbon feedstocks.More allusion quotation Type, the vanadium concentration of heavy hydrocarbon feedstocks is within the scope of 10ppmw to 225ppmw.
Processed hydrocarbon products should have the sulfur content of the reduction of the sulfur content less than heavy hydrocarbon feedstocks, be, for example, less than 1 weight Measure the sulfur content of %.It is recognized, however, that the method for the present invention there can be the ability for making the effective desulfurization of heavy hydrocarbon feedstocks, there is base to provide It is less than 0.5 weight % and the sulphur of the even less than reduction of 0.4 weight % in the gauge relative to the catalyst used in feed volume The processed hydrocarbon products of content.Should also be had using the heavy hydrocarbon feedstocks of the self-activation catalyst treatment of steam activation and be less than heavy hydrocarbon The MCR of the reduction of the MCR of charging, such as 8% or less, preferably 3% or less MCR.
The self-activation catalyst further activated by the method for the invention can be used as the one of arbitrarily suitable reactor assembly Part, make in the case where may include there are hydrogen and the suitable hydroprocessing condition of raised gross pressure and temperature catalyst with again Hydrocarbon charging contacts.This suitable reaction system may include fixed catalyst bed system, boiling catalyst bed system, pulp catalysis Agent system and fluidized catalyst bed systems.Preferred reactor assembly be include the self-activation catalysis being included in reactor vessel The reactor assembly of the fixed bed of agent, the reactor vessel is equipped with anti-for introducing the steam of heavy hydrocarbon feedstocks and appropriate amount The reactor feed entrance tool in device container, such as feed nozzle are answered, and for the abstraction reaction device from reactor vessel The reactor effluent of effluent or processed hydrocarbon products exports tool, such as effluent outlet nozzle.
Activation method of the present invention usually in 2298kPa (300psig) to 20,684kPa (3000psig), preferably 10, 342kPa (1500psig) to 17,237kPa (2500psig), and more preferably in 12,411kPa (1800psig) to 15, It is run under hydrotreating (hydro-conversion and hydrodesulfurization) reaction pressure in 513kPa (2250psig) range.Hydrotreating is anti- Answer temperature usually at 340 DEG C (644 °F) to 480 DEG C (896 °F), preferably at 360 DEG C (680 °F) to 455 DEG C (851 °F), and Most preferably in 380 DEG C (716 °F) to 425 DEG C of (797 °F) ranges.
Heavy hydrocarbon feedstocks are fitted into the flow velocity in the reaction zone of the method for the present invention usually so that providing in 0.01hr-1To 3hr-1 Liquid hourly space velocity (LHSV) (LHSV) in range.Terms used herein " liquid hourly space velocity (LHSV) " refers to that heavy hydrocarbon feedstocks are loaded into the anti-of the method for the present invention It answers the speed in terms of volume/hour in area divided by is fitted into the numerical value of the volume of the catalyst contained in the reaction zone of heavy hydrocarbon feedstocks Than.Preferred LHSV is in 0.05hr-1To 2hr-1, more preferably in 0.1hr-1To 1.5hr-1, and most preferably in 0.2hr-1Extremely 0.7hr-1In range.
It is preferred that hydrogen is fitted into together with heavy hydrocarbon feedstocks and steam in the reaction zone of the method for the present invention.In this case, Hydrogen is sometimes referred to as hydrogen treat gas.Hydrogen treat gas ratio is relative to the heavy hydrocarbon feedstocks amount being fitted into reaction zone Amounts of hydrogen, and usually at most 1781m3/m3In the range of (10,000SCF/bbl).Preferred process gas ratio is in 89m3/ m3(500SCF/bbl) is to 1781m3/m3(10,000SCF/bbl), more preferably in 178m3/m3(1,000SCF/bbl) extremely 1602m3/m3(9,000SCF/bbl), and most preferably in 356m3/m3(2,000SCF/bbl) is to 1425m3/m3(8,000SCF/ Bbl) in range.
Following embodiment is proposed to further illustrate the present invention, but it is not necessarily to be construed as making rising limit to the scope of the invention System.
Embodiment I
This embodiment describes the preparation of catalyst A, representative can be activated further using steam according to the method for the present invention Self-activation catalyst an embodiment.
Catalyst A
Catalyst A is prepared by following steps：First by 2100 parts by weight contain nominal 2% silica aluminium oxide, By dissolving by heating the 63.17 parts by weight nickel nitrate (Ni (NO in 85.04 parts by weight of deionized water3)2), 217.05 parts by weight Molybdenum trioxide (MoO3) powder and 900 parts by weight crushing regeneration Ni/Mo/P hydrotreating catalysts in grinding formula mixing machine and 130 parts by weight, 69.9% concentrated nitric acid and 30 grams of commercial extrusion aids merge.During mixing, 3222.9 parts by weight water will be amounted to add It adds in these components.Component is mixed about 30 minutes.The pH of mixture is 4.12 and LOI is 55.21 weight %.Then it uses 1.3mm trilobal mold extrusioning mixtures, to form 1.3 trilobe-shaped extrudates particles.Then make extrudate at a temperature of 100 DEG C Particle dries period a few hours in air.
Equal portions are dried into extrusion composition granule in air and respectively calcine 2 hour periods at a temperature of 704 DEG C (1300 °F). Finally the mixture through calcining contains 2.2 weight % nickel metals (2.8wt.% in terms of NiO) and 7.9% molybdenum (with MoO3Meter 11.9wt.%) contain the aluminium oxide and 0.7% phosphorus of nominal 2% silica with 83.6 weight %.
The following table 1 illustrates certain properties of the extrusion composition granule through drying and calcination.From the extrudate through calcining shown in table 1 Porous can be seen that bore dia be more than 1000 angstromsMacropore to account for the percentage of total pore volume be at least or to be more than 1% but be less than 10%.Bore dia existsExtremelyThe percentage that hole in range accounts for total pore volume is at least or to be more than 40% but be less than 70%.Moreover, bore dia existsExtremelyThe percentage that hole in range accounts for total pore volume is less than 70%.It is further of importance that noticing that diameter existsExtremelyHole in range accounts for total pore volume at least 10%, and diameter existsExtremelyHole in range accounts at least the 10% of total pore volume.
The property of table 1- catalyst A
Embodiment II
This embodiment describes the preparation of catalyst B, representative can be activated further using steam according to the method for the present invention Self-activation catalyst another embodiment.
Catalyst B
Catalyst B is prepared by following steps：First by 2100 parts by weight of alumina, by dissolving by heating in 85.04 weights Measure 63.17 parts by weight nickel nitrate (Ni (NO in part deionized water3)2), 217.05 parts by weight molybdenum trioxide (MoO3) powder and 900 parts by weight crushing Ni/Mo/P hydrotreating catalysts in grinding formula mixer with 130 parts by weight, 69.9% concentrated nitric acid and 30 Part commercial extrusion aid merges.During mixing, 3222.9 parts by weight water will be amounted to be added in these components.Component is mixed About 30 minutes.The pH of mixture is 4.12 and LOI is 55.21 weight %.Then 1.3mm trilobal mold extrusion mixings are used Object, to form 1.3 trilobe-shaped extrudates particles.Then extrusion composition granule is made to dry a few hours in air at a temperature of 100 DEG C Period.
Dry extrusion composition granule is calcined to about 2 hour time under the maximum temperature of 788 DEG C (1450 °F) in air Section.Finally the mixture through calcining contains 2.2 weight % nickel metals (2.8wt.% in terms of NiO), 7.9% molybdenum (with MoO3 Count 11.9wt.%), 82.6 weight % aluminium oxide and 0.7% phosphorus.
The following table 1 illustrates certain properties through extrusion composition granule that is dry and calcining.The extrusion through calcining shown in the table 1 The porous of object can be seen that bore dia and be more thanMacropore account for total pore volume percentage be less than 20%, directly Diameter is more thanKong Zhanqi pore volumes at least 1%, and bore dia existsExtremelyHole in range The percentage for accounting for total pore volume is more than 90%.Bore dia intermediate value at least more thanAnd it is less than
The property of table 2- catalyst B
Embodiment III
In this embodiment, hydrogen is added using the self-activation catalyst with the composition and property similar with catalyst A Handling has the demetalization of the distillating property (being measured by ASTM method D 7169) and other properties that are shown in table 3 and 4 Arabic (Arabian) residual oil.
The distillating property of table 3- demetalizations Arab residual oil
Wt.% Temperature (°F)
IBP 315
10 582
20 693
30 777
40 848
50 918
60 990
70 1069
80 1159
90 1283
FBP 1351
Other properties of table 5-charging
H (wt%) 12.16
C (wt%) 86.60
N (wt%) 0.18
S (wt%) 1.06
Ni(ppm) 8
V(ppm) 17.5
GN(ppm) 462
MCR 6.7
1000F+, wt% 38.7
C7-Asphalitine, wt% 2.2
Density 0.9322
C5Asphalitine, wt% 3.5
By the demetalization Arab resid feed with above-mentioned property be packed into together with hydrogen load have with catalyst A In the reactor of the self-activation hydrotreating catalyst of similar composition and property.Reactor is maintained to about 130 bars of pressure Under power, and to provide 0.5hr-1The rate of liquid hourly space velocity (LHSV) (LHSV) be packed into resid feed, while with 590Nm3/m3H2/ oil ratio Rate is packed into hydrogen.The temperature of reactor is set as 373.9 DEG C (705 °F).Continuous operation is more than 4000 hours.
Before operation during 3,100 hours, self-activation catalyst is not contacted with steam.From the 3,100th hour to 4,000 hours, self-activation catalyst is made to be contacted with steam, ratio of the steam based on resid feed weight meter is 3.27wt.% steam.It is interrupted after the 4000th hour and uses steam.
It is illustrated in Fig. 1 in the case where addition is not with steam is added, in the hydrotreating of demetalization Arab residual oil The figure of weight % is converted by the total sulfur that self-activation catalyst A is realized.It will be seen from figure 1 that (it is indicated certainly sulphur conversion percentages The activity of activated catalyst) it is running until steadily being improved in the 2500th hour first part, then at the 2nd, 500 hour With the 3,000th hour between start stablize in about 60wt.%.However, at the about the 3100th hour into resid feed Steam is added, the sulphur activity of conversion of self-activation catalyst is significantly improved to about 70wt.%, this is quite to make us unexpected. When interrupting addition steam at the about the 4th, 000 hour, sulphur conversion ratio is back to the about 60wt.% water undergone before steam addition It is flat, this confirms that the addition of steam is the reason of activity further increases.
It is illustrated in Fig. 2 in the case where addition is not with steam is added, in the hydrotreating of demetalization Arab residual oil The figure of weight % is converted by micro- carbon residue (MCR) that self-activation catalyst A is realized.Figure it is seen that in operation until the During 3,100 hours first parts, MCR activity of conversion is about 20wt.% to 30wt.%.However, small the about the 3rd, 100 When at into resid feed add steam after, the MCR activity of conversion of self-activation catalyst is significantly improved to surprising 70wt.% to 80wt.%.When interrupting addition steam at the about the 4th, 000 hour, MCR conversion ratios are back to be added in steam 20wt.% to the 30wt.% ranges undergone before adding.

Claims (7)

1. a kind of method for activating the self-activation hydrotreating catalyst used in handling heavy hydrocarbon feedstocks, the method packet Including makes the self-activation hydrotreating catalyst be contacted with steam in the presence of the heavy hydrocarbon feedstocks,
The wherein described self-activation hydrotreating catalyst includes：By following steps manufacture comprising co-milled mixtures through forging The particle of burning：Inorganic oxide powder, molybdenum trioxide powder and nickel compound are co-mulled and made into, the co-milled mixtures are then made Particle is formed, calcines the particle thus to provide the particle through calcining, wherein the molybdenum trioxide powder is with small In 500 microns of maximum sized fine particle form, the particle through calcining includes based on metal and based on described through forging Molybdenum existing for amount of the total weight of the particle of burning within the scope of 1 weight % to 10 weight %, and so that nickel-is p- described Nickel existing for amount of the weight ratio of molybdenum less than 0.4, and the wherein described particle through calcining has following pore-size distribution：So that institute Diameter in the particle through calcining is stated to existExtremelyHole in range accounts for the total pore volume of the particle through calcining Less than 70%, diameter exists in the particle through calciningExtremelyHole in range accounts for the particle through calcining Total pore volume at least 10%, and diameter is more than in the particle through calciningHole account for it is described through calcining The 1% to 10% of the total pore volume of particle,
Wherein the controlled burnout of the calcining in 450 DEG C (842 °F) to 900 DEG C of (1652 °F) ranges at a temperature of effectively carried For with regulation pore structure the self-activation catalyst calcination time section,
The heavy hydrocarbon feedstocks wherein handled through the self-activation hydrotreating catalyst have in 1ppmw to 250ppmw ranges Interior nickel content, the content of vanadium within the scope of 5ppmw to 250ppmw and the sulfur content within the scope of 2wt.% to 8wt.%.
2. the method as described in claim 1 contacts wherein being based on the heavy hydrocarbon feedstocks weight meter with the self-activation catalyst Steam amount within the scope of 0.01wt.% to 10wt.%.
3. method as claimed in claim 2, wherein making the heavy hydrocarbon feedstocks be connect with the self-activation hydrotreating catalyst Before touching, the steam is added in the heavy hydrocarbon feedstocks.
4. method as claimed in claim 2, wherein the steam is added to the reactor containing the self-activation catalyst In container.
5. the method as described in claim 1, wherein making the heavy hydrocarbon feedstocks be connect with the self-activation hydrotreating catalyst Before touching, water is added in the heavy hydrocarbon feedstocks being enough at a temperature of making water be converted to steam.
6. the method as described in claim 1 contacts wherein being based on the heavy hydrocarbon feedstocks weight meter with the self-activation catalyst Steam amount within the scope of 2wt.% to 6wt.%.
7. the method as described in claim 1, wherein controlled in 700 DEG C (1292 °F) to 790 DEG C of (1454 °F) ranges is forged At a temperature of burning, the self-activation hydrotreating catalyst calcining comprising the particle through calcining is effectively provided and is tied with regulation hole The calcination time section of the self-activation catalyst of structure.
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